Novel oxime ethers, the preparation thereof, compositions containing them and the use thereof

ABSTRACT

The invention relates to novel oxime ethers of the formula I ##STR1## wherein R 1  is hydrogen, halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, lower alkylthio, lower haloalkylthio, lower alkylsulfinyl, lower alkylsulfonyl, lower haloalkylsulfinyl, lower haloalkylsulfonyl or nitro, each of R 2  and R 3  is hydrogen, halogen, lower alkyl, lower alkoxy or lower haloalkoxy, and Q is an unsubstituted or substituted lower alkyl, lower alkenyl, lower alkynyl or cycloalkyl group, a lower alkanoyl radical, an aliphatic, cycloaliphatic, aromatic or heterocyclic acyl radical which may be substituted or unsubstituted, a carbonyl or thiocarbonyl radical, an aryl or aralkyl radical, an acylimidomethyl radical, a phthalimidomethyl radical or a heterocyclic radical. 
     These compounds are able to act as antidotes or safeners for protecting cultivated plants from the phytotoxic action of aggressive herbicides. Preferred crops are sorghum, cereals, maize and rice, and herbicides are chiefly chloroacetanilides and thiocarbamates.

The present invention relates to novel oxime ethers, to the preparationthereof, to compositions for protecting cultivated plants from thephytotoxic effects of herbicides, which compositions contain the noveloxime ethers as active component, and to the use thereof.

It is known that herbicides belonging to a very wide range of compoundclasses such as triazines, urea derivatives, carbamates, thiocarbamates,haloacetanilides, halophenoxyacetic acids etc., when employed in aneffective concentration, often also damage cultivated plants to acertain extent in addition to the weeds which it is desired to control.Too high concentrations are often applied unintentionally and randomlywhenever peripheral zones overlap on zonal spraying, whether as aconsequence of the action of wind or through miscalculating the sweep ofthe spray device employed. The climatic conditions or the nature of thesoil may be such that the concentration of herbicide reommended fornormal conditions acts as an overdose. The quality of the seeds may alsobe a factor in the tolerance of the herbicide. To counteract thisproblem, different compounds have already been proposed which are ablespecifically to antagonise the harmful action of the herbicide on thecultivated plant, i.e. to protect the cultivated plant withoutnoticeably influencing the herbicidal action on the weeds to becontrolled. However, it has been found that the proposed antidotes veryoften have a species-specific activity both with respect to thecultivated plants and to the herbicide and also, in some cases,contingent on the mode of application, i.e. a specific antidote is oftensuitable only for a specific cultivated plant and a few classes ofherbicides.

For example, British patent specification No. 1,277,557 describes theprotective treatment of seeds or seedlings of wheat and sorghum withcertain oxamic acid esters and amides against attack by "ALACHLOR"(N-methoxymethyl-N-chloroacetyl-2,6-diethylaniline). Antidotes fortreating cereals, maize and rice seeds against the harmful effects ofherbicidal thiocarbamates are proposed in German Offenlegungsschriftspecifications Nos. 1,952,910 and 2,245,471 and in French patentspecification No. 2,021,611. German patent specification No. 1 576 676and U.S. Pat. No. 3,131,509 disclose the use of hydroxyaminoacetanilidesand hydantoins for protecting cereal seeds against the effects ofcarbamates.

The direct pre- or postemergence treatment of certain useful plants withantidotes as antagonists of specific classes of herbicides in a croparea is disclosed in German Offenlegungsschrift specifications Nos.2,141,586 and 2,218,097 and in U.S. Pat. No. 3,867,444.

Further, German Offenlegungsschrift No. 2,402,983 discloses that maizeplants can be effectively protected against damage by chloroacetanilidesby adding an N-disubstituted dichloroacetamide as antidote to the soil.

According to German Offenlegungsschrift specification Nos. 2,808,317 and2,837,204, alkoxyiminobenzylcyanides, in which the alkoxy group isdifferently substituted, can also be used as antidotes for protectingcultivated plants from the harmful effects of herbicides belonging todifferent classes of compounds.

The present invention relates to novel oxime ethers of the formula I##STR2## wherein R₁ is hydrogen, halogen, lower alkyl, lower haloalkyl,lower alkoxy, lower haloalkoxy, lower alkylthio, lower haloalkylthio,lower alkylsulfinyl, lower alkylsulfonyl, lower haloalkylsulfinyl, lowerhaloalkylsulfonyl or nitro,

R₂ and R₃ are each hydrogen, lower alkyl, lower alkoxy or lowerhaloalkyl,

Q is lower alkyl which is straight chain or branched or interrupted byhetero atoms and is substituted

(a) by halogen atoms or by the cyano or oxy group, or

(b) by a phenoxy or thiophenoxy group, or is also lower alkenyl orhaloalkenyl; lower alkynyl or haloalkynyl; a 3- to 7-memberedcycloalkylcarbamoyl a lower alkanoyl radical; a lower alkenoyl radical;a lower alkyl carbamoyl or hydrazidocarbonyl radical; a lower alkylthiocarbamoyl radical; a lower alkylthiocarboxy radical; a loweralkanoyl radical or a salt thereof; an aliphatic or araliphatic acylradical; a halogen-substituted aliphatic acyl radical; an aliphatic acylradical which is substituted by alkoxy or phenoxy; a cycloaliphatic,aromatic or heterocyclic acyl radical; a substituted or unsubstitutedaryl radical; an aliphatic, cycloaliphatic or aromatic carbonic acidradical; an aliphatic, cycloaliphatic or aromatic thiocarbonic acidradical; a carbamoyl radical; an alkyl or arylsulfonyl radical; analkoxyalkylsulfamoyl or sulfamoyl radical; a halogen-substitutedalkylsulfonyl or arylsulfonyl radical; a cyclic acylamidomethyl radical##STR3## wherein A is an alkylene chain, a halogenated alkylene chain,an alkenyl chain or a halogenated alkenyl chain; a phthalimidomethylradical which may be partially or completely saturated and may besubstituted in the phenyl nucleus as indicated for R₁, R₂ and R₃ ; a 5-or 6-membered saturated, partially saturated or aromatic heterocyclicring which may contain 1 to 3 nitrogen, oxygen and/or sulfur atoms andmay be substituted as indicated for R₁, R₂ and R₃ ; and

X is a fluorinated C₁ -C₃ alkyl radical which may also contain chlorine.

Halogen denotes fluorine, chlorine, bromine and iodine, with fluorineand chlorine being preferred.

The fluorinated alkyl radical X may be e.g. difluoromethyl,trifluoromethyl, chlorodifluoromethyl, tetrafluoroethyl,pentafluoroethyl, difluorochlorofluoroethyl and heptafluoropropyl. Amongthese radicals X, perfluorinated alkyl radicals are preferred in whichone fluorine atom may be replaced by a chlorine atom. Paticularlypreferred radicals X are trifluoromethyl, chlorodifluoromethyl,pentafluoroethyl and difluoromethyl.

Alkyl by itself or as moiety of another substituent comprises branchedor unbranched C₁ -C₈ alkyl groups. Lower alkyl is C₁ -C₄ alkyl, e.g.methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, as well as the higher homologues amyl, isoamyl, hexyl,heptyl, octyl and the isomers thereof. By analogy, alkanoyl orcyanoalkyl groups contain an additional carbon atom. A lower alkanoylradical consists of a lower alkyl moiety containing 1 to 4 carbon atoms,the carbonyl group and an alcoholic or phenolic radical of 1 to 8 carbonatoms. Examples are in particular: acetic acid esters --CH₂ --COO--C₁-C₈ --alkyl, --CH₂ --CO--C₃ -C₄ alkenyl, --CH₂ --COO--C₃ -C₄ -alkynyl or--CH₂ --OO--phenyl, wherein the phenyl radical may be substituted by R₁,R₂ and R₃, and also CH₂ --COS--C₁ -C₈ alkyl, --CH₂ --COS--C₃ -C₄ alkenylor --CH₂ --COS--C.sub. 3 -C₄ alkynyl, and also the corresponding1-propionic acid esters --CH(CH₃)--COT (T=a C₁ -C₈ alkoxy, C₁ -C₈alkylthio, C₃ -C₄ alkenyloxy, C₃ -C₄ alkenylthio, C₃ -C₄ alkynyloxy, C₃-C₄ alkynylthio radical or a phenoxy radical which is unsubstituted orsubstituted by R₁, R₂ and R₃). Alkenyl radicals are aliphatic radicalscontaining one or two double bonds ("alkadienyl radicals") and a maximumof 6, preferably 4, carbon atoms. Haloalkenyl radicals contain up to 3halogen atoms, preferably chlorine or bromine. Lower alkynyl is propynyl(=propargyl) and butynyl.

A lower alkenoyl radical consists accordingly of a lower alkenyl moietycontaining 3 to 4 carbon atoms, the carbonyl group and an alcoholic orphenolic moiety containing 1 to 8 carbon atoms. Examples are inparticular the butenoyl and pentenoyl radicals --CH₂ --CH═CH--COT, CH₂--CH(CH₃)═CH--COT, CH(CH₃)═CH═CH--COT, wherein T is as defined above. Alower alkanoyl radical or a salt thereof consists of a lower alkylmoiety of 1 to 4 carbon atoms and the carboxyl group or a salt thereofwith an alkali metal, alkaline earth metal, iron or copper ion or withthe cation of a quaternary ammonium group.

Alkanecarbonamide radicals comprise also monosubstituted orsymmetrically or unsymmetrically disubstituted radicals, thesubstituents of which may be selected from lower alkyl, lower alkenyl,propynyl or butynyl, as well as one cycloalkyl or phenyl ring which maybe substituted as indicated for R₂ /R₃ or unsubstituted. Examples ofsuch radicals are the acetamido radical --CH₂ CONH₂, the acetothiamidoradical --CH₂ CSNH₂, or the corresponding radicals in which one or bothradicals are replaced by lower alkyl, lower alkenyl, lower alkynyl,cycloalkyl or phenyl, and also the corresponding propion-1-ylamidoradicals --CH(CH₃)CONH₂ and propion-1-ylthioamido radical--CH(CH₃)--CS--NH₂. Also comprised are the acylated alkanecarbonamidesradicals such as the acetoacetamide radical --CH₂ CONHCOCH₃, thepropion-1-ylacetamido radical --CH(CH₃)CONHCOCH₃, the acetoureidoradical --CH₂ CONHCO--NH₂, the propion-1-ylureido radical--CH(CH₃)CONHCONH₂, which radicals may be substituted symmetrically orunsymmetrically at the nitrogen atom by lower alkyl, lower alkenyl,lower alkynyl, cylcoalkyl or phenyl, and also the acetoformamido orpropion-1 -ylformamido radical and the acetohydrazido orpropion-1-ylhydrazido radical.

An aliphatic, araliphatic, cycloaliphatic or aromatic acyl radicalconsists of a carbonyl group which is linked to a C₁ -C₈ alkyl group, ahalogenated alkyl group, an alkoxy group, a halogenated alkoxy group, aC₃ -C₆ alkenyl group, a halogenated alkenyl group, an alkenyloxy group,a halogenated alkenyloxy group, a C₃ -C₆ alkynyl group, a halogenatedalkynyl group, an alkynyloxy group, a halogenated alkynyloxy group, a C₃-C₈ cycloalkyl group, a halogenated C₃ -C₈ cycloalkyl group, ahalogenated cycloalkyl group or a phenyl group which is unsubstituted orsubstituted by R₁, R₂ and R₃. Representative examples of such radicalsare: acetyl, propionyl, neopentamoyl, 1,1-dichloropropionyl, crotonyl,2-methylcrotonyl, chloroacetyl, 1,1-dimethyl-2-chloropropionyl,dichloroacetyl, trifluoroacetyl, acroyl, methacroyl, dimethylacroyl,1,2,2-trichloroacroyl, dibromoacroyl, α-bromoacroyl, methyloxalyl,ethyloxolyl, amidooxalyl, methoxyacetal, phenoxyacetyl,1-(phenoxy)-propionyl, 1-(4-chlorophenoxy)propionyl,1-(2-chlorophenoxy)propionyl, 1-(2,4-dichlorophenoxy)propionyl,1-(4-chloro-2-methylphenoxy)propionyl, phenylthioacetyl,1-(4-chlorophenylthio)acetyl, phenylacetyl, 4-chlorophenylacetyl,3-methyl-1-phenylbutyryl, 3-methyl-1-p-chlorophenylbutyryl,2,2-dimethylcyclopropylcarbonyl, cyclopropylcarbonyl,2,2-dichlorocyclopropylcarbonyl, 1-methylcyclopropylcarbonyl,cyclopentylcarbonyl, cyclohexylcarbonyl, benzoyl, 2-methylbenzoyl,3-trifluoromethylbenzoyl, 2-trifluoromethylbenzoyl,4-difluorochloromethylbenzoyl, 2-nitrobenzoyl, 4-chlorobenzoyl,3-chlorobenzoyl, 4-amisoyl, 3-acetoxybenzoyl, 3-methyl-4-nitrobenzoyl.

A heterocyclic acyl radical consists of the carbonyl group which islinked to a heterocyclic radical. Such radicals are saturated, partiallysaturated or heteroaromatic 5- or 6-membered radicals which contain 1 to3 nitrogen, oxygen or sulfur atoms and which may be substituted byhalogen atoms, lower alkyl, or as indicated for R₁, R₂ and R₃, and whichmay also contain oxo or sulfoxo groups.

Examples of such radicals are: nicotinoyl, isonicotinoyl,1,3-dichloro-4-pyridinecarbonyl; thiophene-2-carbonyl; 2-furoyl,4-methyl-1,2,3-thiadiazol-5-carbonyl, 4-(2,5-dimethyl)furoyl,4-(3,5-dimethyloxazole)carbonyl,3-(2-methyl-2,3-dihydro-4(H)-pyran)carbonyl,2-(3-methyl-3,4-dihydro-1,4-thioxan)carbonyl,2-(3-methyl-3,4-dihydro-1-oxo-1,4-thioxan)carbonyl,2-(2,4-dimethylthiazole)carbonyl, 2-thiazolecarbonyl,4-(2,4-dichloropyrimidine)carbonyl, 2-(3-bromo)furoyl,2-(4-nitro)furoyl, 2-(3-methyl)furoyl, 2-(3-chloro)thiophenecarbonyl,4-pyridazinocarbonyl, 4-piperidinocarbonyl,2-(4-methyl)-piperidinocarbonyl, 2-morpholinocarbonyl,2-thiomorpholinocarbonyl, 2-pyrrolocarbonyl, 2-tetrahydrofuroyl,2-oxazoyl, 3-pyrazolylcarbonyl, 2-pyrrolocarbonyl,2-pyrrolidinocarbonyl.

C₃ -C₇ Cycoalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and cycloheptyl. Cycloaliphatic radicals correspond to thesering systems but, where possible, may also additionally contain one ormore double bonds.

An araliphatic radical comprises an aryl group such as phenyl which ismono- to trisubstituted as indicated for R₁, R₂ and R₃, or alsonaphthyl, fluorenyl or indanyl which is linked through lower alkyl orlower alkenyl to the residue of the molecule. Examples are benzyl,phenethyl, phenylallyl, 4-chlorobenzyl, 3,4-chlorobenzyl,3-trifluorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 3-bromobenzyl,4-cyanobenzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 2-fluorobenzyl,2-fluorophenylethyl, 2-nitrobenzyl, 4-methoxybenzyl, 3-methoxybenzyl,4-phenylbenzyl, 4-fluorobenzyl.

Examples of aliphatic chains interrupted by hetero atoms aremethoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, propoxyethyl,butoxyethyl, methoxypropyl, methylthioethyl, ethylthioethyl,methylthiopropyl, methylaminoethyl, tert-butylaminoethyl,methoxyethoxyethyl, ethoxyethoxyethyl.

A carbamoyl radical or a thiocarbamoyl radical carries at the nitrogenatom either hydrogen or one or two radicals selected from the groupconsisting of lower alkyl, lower alkoxyalkyl, lower alkenyl, lowerhaloalkenyl, alkynyl or a hydrogen atom, and alternatively a C₃ -C₆cycloalkyl ring or a phenyl ring which may be substituted as indicatedfor R₁, R₂ and R₃ or unsubstituted. Examples of such radicals are:carbamoyl, methylcarbamoyl, ethylcarbamoyl, cyclohexylcarbamoyl,n-propylcarbamoyl, anilido, 2,6-dimethylanilido, 4-chloroanilido,4-methoxyanilido, 3-trifluoromethylanilido, isopropylcarbamoyl,tert-butylcarbamoyl, thioanilido, 4-methylthioanilido.

A sulfoxyl radical consists of the sulfoxy group and an unsubstituted orhalogenated C₁ -C₈ alkyl radical or a phenyl radical which may besubstituted as indicated for R₁, R₂ and R₃. Examples of such radicalsare methylsulfonyl, chloromethylsulfonyl, trifluoromethylsulfonyl,phenylsulfonyl, 4-chlorophenylsulfonyl, 4-tolylsulfonyl,4-trifluoromethylphenylsulfonyl, trichloromethylsulfonyl.

A sulfamoyl radical carries at the nitrogen atom either hydrogen orpreferably two radicals selected from the group consisting of loweralkyl, lower alkoxyalkyl, lower alkenyl or C₄ -C₅ alkylene which may beinterrupted by oxygen or sulfur. Examples of such radicals are:dimethylsulfamoyl, piperidinosulfonyl, morpholidosulfonyl.

A cyclic acylamidomethyl radical consists of thedicarbonylimidomethylene moiety and an alkylene, halogenated alkylene,alkenylene or halogenated alkenylene chain. Examples of such radicalsare malonylimidomethyl, maloylimidomethyl, succinylimidomethyl,glutanylimidomethyl, fumaroylimidomethyl,2,3-dimethylfumaroylimidomethyl, 2,3-dichlorofurmaroylimidomethyl.

The phthalimidomethyl radicals may be both substituted in the phenylnucleus as indicated for R₁, R₂ and R₃ and partially or completelysaturated, and are accordingly, 3,4-dihydrophthalimidomethyl andtetrahydrophthalimidomethyl radicals.

Heterocyclic radicals are monocyclic and bicyclic rings containing 1 to3 identical or different hetero atoms O, S and N. Representativeexamples are 3- to 6-membered, preferably 5- or 6-membered, heterocyclicrings which may be saturated, partially saturated or unsaturated andsubstituted as indicated for R₁, R₂ and R₃ or unsubstituted. Withoutimplying any limitation, representative examples of such rings are:furan, nitrofuran, bromofuran, methylfuran, thiophene, chlorothiophene,pyridine, 2,6-dichloropyridine, pyrimidine, pyridazine, pyrazine,piperidine, methylpiperidine, morpholine, thiomorpholine,tetrahydrofuran, oxazole, pyrazole, pyrrole, pyrroline, pyrrolidine,thiazole, 2,3-dihydro-4-H-pyrane, pyrane, dioxan, 1,4-oxathia(2)-ine,quinoline, indole, benzthiazole, benzoxazole, benzimidazole.

Particularly important oximes of this invention are the compounds of theformula Ia ##STR4## wherein R₁, R₂, Q and X are as defined for formulaI. Among this group of oximes, those compounds are especially preferredin which X is the trifluoromethyl group and which have the formula Ib##STR5## wherein R₁, R₂ and Q are as defined for formula I.

Oxime ethers having pronounced biological properties are those of theformula Ic ##STR6## wherein R₁ and R₂ are as defined for formula I andQ' is C₁ -C₄ alkyl, preferably methyl, ethyl, propyl and butyl and alsocyclopropyl, C₃ -C₄ alkenyl such as allyl, C₁ -C₄ cyanoalkyl such ascyanomethyl and cyanoeth-1-yl, carbamoyl, C₁ -C₄ carbamoylalkyl such ascarbamoylmethyl or carbamoyleth-1-yl, C₁ -C₄ alkylcarbamoyl, di(C₁ -C₄alkyl)carbamoyl.

Preferred individual compounds are in particular:

1-phenyl-1-methoximino-2,2,2-trifluoroethane,

1-(3-trifluoromethylphenyl-1-cyclopropylmethoximino-2,2,2-trifluoroethane,

1-(4-chlorophenyl)-1-n-propoximino-2,2,2-trifluoroethane,

1-(4-chlorophenyl)-1-allyloximino-2,2,2-trifluoroethane,

1-phenyl-1-carbamoylmethoximino-2,2,2-trifluoroethane,

1-(4-fluorophenyl)-1-carbamoylmethoximino-2,2,2-trifluoroethane,

1-(4-chlorophenyl)-1-carbamoylmethoximino-2,2,2-trifluoroethane,

1-(3-trifluoromethyl)-1-carbamoylmethoximino-2,2,2-trifluoroethane,

1-phenyl-1-carbamoylmethoximino-2,2,3,3,3-pentafluoropropane,

1-phenyl-1-carbamoyleth-1-oximino-2,2,2-trifluoroethane,

1-(4-chlorophenyl)-1-carbamoyleth-1'oximino-2,2,2-trifluoroethane,

1-(3-trifluoromethylphenyl)-1-carbamoyleth-1'-oximino-2,2,2-trifluoroethane

1-(4-chlorophenyl-1-N-n-propylcarbamoyloximino-2,2,2-trifluoroethane,

1-(3-chlorophenyl)-1-carbamoylmethoximino-2,2,2-trifluoroethane,

1-(3-chlorophenyl)-1-isopropyloxycarbamoylmethoximino-2,2,2-trifluoroethane.

The novel oxime ethers of this invention are prepared by reacting a saltof an oxime of the formula II ##STR7## wherein M is an alkali metalcation or an alkaline earth metal cation and R₁, R₂, R₃ and X are asdefined above, with a reactive ester of the formula III

    Y--Q                                                       (III)

wherein Q is as defined for formula I and Y is the radical of an organicor inorganic acid.

Suitable salts of an oxime of the formula II are in particular thesodium and potassium salts. The reaction of the oxime of the formula IIwith the reactive ester of the formula III is conveniently carried outin an inert organic solvent. Particularly suitable solvents are polarsolvents such as acetonitrile, dimethylformamide, dimethylacetamide,methylpyrrolidone and dimethylsulfoxide. The reactants are normallyemployed in equimolar amount. However, an excess of one or otherreactant may also be used to bring the reaction to completion.Particularly suitable reactive acid radicals are the halides and alsosulfonic acid radicals of e.g. methylsulfonic acid, ethylsulfonic acid,phenylsulfonic acid or toluenesulfonic acid. The reaction isconveniently carried out in the temperature range from 60° to 90° C. Ifanother solvent is used, e.g. toluene or chlorobenzene, then thereaction is carried out at higher temperature and the reaction time islonger.

According to U.S. Pat. No. 4,260,555, the radical Q is esterified with asulfonic acid radical and the resultant ester of the formula IV

    Z--SO.sub.3 --Q                                            (IV)

wherein Z is a lower alkyl radical or a phenyl radical substituted bylower alkyl or halogen, is reacted with the hydroxyoxime of the formulaII or a salt thereof.

The oximes of formula II may be prepared in known manner by reacting thecorresponding ketones with hydroxylamine. The ketones required for thereaction can in turn be obtained by reacting a Grignard compound of theformula V ##STR8## wherein Y is chlorine, bromine or iodine, and R₁, R₂and R₃ are as defined above, with a carboxylic acid X--COOH or a saltthereof, an acid chloride X--COCl or a nitrile X--CN, each derived fromthe radical X as defined above (cf. U.S. Pat. No. 3,748,361). Further,it is also possible to obtain ketones suitable for preparing the oximesof formula II by reacting a benzene of the formula VI ##STR9## in whichR₁, R₂ and R₃ are as defined above, with a carboxylic acid chlorideX--COCl derived from the radical X as defined above, in the presence ofaluminium chloride.

Examples of oximes of the formula II which are suitable for obtainingthe novel oxime ethers of the formula I are:

1-phenyl-1-hydroximino-2,2,2-trifluoroethane

1-(4-methylphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-chlorophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-fluorophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-trifluoromethylphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3-trifluoromethylphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-methoxyphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-trifluoromethoxyphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3-nitrophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3,4-dimethylphenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3,4-dichlorophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(4-chlorophenyl)-1-hydroximino-2,2-difluoroethane

1-(4-chlorophenyl)-1-hydroximino-2-chloro-2,2-difluoroethane

1-(4-methoxyphenyl)-1-hydroximino-2-chloro-2,2-difluoroethane

1-(4-trifluoromethoxyphenyl)-1-hydroximino-2-chloro-2,2-difluoroethane

1-(3-nitrophenyl)-1-hydroximino-2-chloro-2,2-difluoroethane

1-phenyl-1-hydroximino-2,2,3,3,3-pentafluoropropane

1-(4-methylphenyl)-1-hydroximino-2,2,3,3,3-pentafluoropropane

1-(4-chlorophenyl)-1-hydroximino-2,2,3,3,3-pentafluoropropane

1-(3-nitrophenyl)-1-hydroximino-2,2,3,3,3-pentafluoropropane

1-phenyl-1-hydroximino-2,2,3,3,4,4,4-heptafluorobutane

1-(4-chlorophenyl)-1-hydroximino-2,2,3,3,4,4,4-heptafluorobutane

1-(2-chlorophenyl)-1-hydroximino-2,2,2-trifluoroethane

1-(3-chlorophenyl)-1-hydroximino-2,2,2-trifluoroethane.

Suitable reactive esters of the formula III are in particular thehalides and sulfonic acid esters corresponding to the definition of Q,substituted lower alkyl groups, lower alkenyl or alkynyl groups orcycloalkyl groups, and also alkanecarboxylic acid derivatives which arehalogenated or sulfonated in the alkyl moiety; and arylhalides,arylsulfonates, arylkylhalides or aralkylsulfonates; the halides ofcarbonic acid esters or thiocarbonic acid esters, alkylsulfonyl orarylsulfonyl halides, or a halide of a sulfamoyl group; and also thehalomethyl or sulfonylmethyl derivatives of acyliminomethyl orphthalimidomethyl groups; and halides or sulfonyl esters of heterocyclicradicals which correspond to the definition of Q.

Such compounds are known or may be prepared e.g. by reaction withhalogenating agents such as sulfuryl chloride or sulfuryl bromide,thionyl chloride or thionyl bromide, phosphoroxy chloride or phosphorylester chloride or the corresponding bromides, or with a concentratedhydrohalic acid or by reaction with halides or anhydrides of sulfonicacids.

The novel oxime ethers of formula I are most suitable for protectingcultivated plants from damage caused by agrochemicals. This protectionextends in particular to herbicides of different compound classes,including 1,3,5-triazines, 1,2,4-triazines, phenylurea derivatives,carbamates, thiocarbamates, phenoxyacetates, phenoxypropionates,haloacetanilides, halophenoxyacetates, substitutedphenoxyphenoxyacetates and phenoxyphenoxypropionates, substitutedpyridyloxyphenoxyacetates and pyridyloxyphenoxypropionates, benzoic acidderivatives etc., where these compounds are not tolerated or areinsufficiently tolerated by cultivated plants. The novel oxime ethers offormula I are suitable in particular for protecting cultivated plantsfrom the harmful effects of haloacetanilides and thiocarbamates. Theycan therefore be termed antidotes or also safeners with respect to theiruse in combination with the herbicides referred to above.

The compounds of the formula I exist in different stereoisomeric forms,viz. the syn- and anti-forms of the basic oximes and also individualenantiomers of such compounds which contain a centre of asymmetry in theradical Q. These stereoisomers also fall within the province of theinvention.

Depending on the end use, the safener of antidote of the formula I canbe used for pretreating seeds of the cultivated plant (dressing of theseeds or seedlings) or it can be added to the soil before or aftersowing. However, it can also be applied pre- or post-emergence by itselfalone or together with the herbicide. The treatment of the plant orseeds with the antidote can therefore in principle be carried outindependently of the time of application of the phytotoxic chemical. Itcan, however, also be carried out by simultaneous application ofphytoxic chemical and antidote (tank mixture). The pre-emergencetreatment includes both treatment of the crop area before sowing(ppi=pre-plant incorporation) and treatment of the crop areas aftersowing but before emergence of the plants.

The rates of application of the antidote with respect to the herbicidedepend largely on the mode of application. Where a field treatment iscarried out, either simultaneously as tank mixture or with separateapplication of herbicide and antidote, the ratio of antidote toherbicide is in the range from 1:100 to 5:1. Full protective action isusually obtained at a ratio of antidote to herbicide of 1:1 to 1:20.When dressing seeds and taking similar specific protective measures,however, much lower amounts of antidote are required compared with e.g.the amounts of herbicide later employed per hectare of crop area. Forseed dressing, 0.1 to 10 g of antidote per kg of seeds are required.Full protection is usually obtained with 0.1 to 2 g of antidote per gramof seeds. If it is desired to apply the antidote shortly before sowingby seed pretreatment, antidote solutions which contain the activeingredient in a concentration of 1 to 10,000 ppm are used. Fullprotective action is normally obtained ith antidote concentrations of100 to 1000 ppm.

As a rule there is a substantial interval of time between protectivemeasures such as seed dressing and treatment of seedlings with anandidote of the formula I and the possible later field treatment withagricultural chemicals. Pretreated seeds and plants can later come incontact with different chemicals in agriculture, horticulture andforestry. Accordingly, the invention relates to plant protectioncompositions which contain an antidote of the formula I as activeingredient, together with conventional carriers. If appropriate, suchcompositions may be additionally mixed with the chemical against whoseeffects it is desired to protect the cultivated plant.

Cultivated plants within the scope of this invention are all plantswhich, in any form, can be harvested (seeds, roots, stalks, tubers,leaves, blossoms) and from which extracts can be obtained (oils, sugar,starch, protein) and which are cultivated for this purpose.

These plants comprise e.g. all species of cereals such as wheat, rye,barley, oats and, in particular, rice, sorghum, maize, and also cotton,sugar beet, sugar cane, soybeans, beans, and peas.

The antidote can be employed wherever it is desired to protect acultivated plant of the kind indicated above from the harmful effects ofan agricultural chemical. As already mentioned, possible agriculturalchemicals are primarily herbicides of the most widely varying compoundclasses, in particular haloacetanilides and thiocarbamates.

Numerous haloacetanilides whose harmful effects on cultivated plants canbe antagonised with the novel oxime ethers of the formula I are known inthe art (q.v. German patent applications Nos. 2,305,495; 2,328,340;2,212,268; 2,726,252 and 2,805,757; and U.S. Pat. Nos. 3,946,044;4,022,608 and 4,039,314). Such haloacetanilides may be illustrated bythe general formula VII ##STR10## wherein Hal is halogen, preferablychlorine or bromine, each of R₄ and R₅ independently of the other ishydrogen, halogen, lower alkyl, alkoxy, alkylthio, haloalkyl,alkoxyalkyl or alkylthioalkyl, Z is hydrogen, halogen, lower alkyl,alkoxy, alkylthio, haloalkyl, alkoxyalkyl or alkylthioalkyl, whichradicals Z are preferably in the 3-position with respect to the nitrogenatom, n is 0 to 3, A is alkylene, preferably methylene, 1,1-ethylene,and 1,2-ethylene which may be substituted by 1 or 2 lower alkyl groups,and R₆ is lower alkoxy, hydroxycarbonyl, alkoxycarbonyl, carbamoyl,N-alkylcarbamoyl, N,N-dialkylcarbamoyl, cyano, an unsubstituted orsubstituted nitrogen-containing heterocyclic radical, alkanoyl,unsubstituted or substituted benzoyl, unsubstituted or substituted1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-3-yl or1,3,4-triazol-1-yl.

Typical examples of such haloacetanilides are:

N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-methoxymethyl-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2,6-dimethylaniline

N-(2-allyloxyethyl)-N-chloroacetyl-2,6-dimethylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-isopropoxyethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(methoxyethyl)-2,6-diethylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-methylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline

N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methylaniline

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline

N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methylaniline

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-dimethylaniline

N-ethoxycarbonylmethyl-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-methoxycarbonylmethyl-2,6-dimethylaniline

N-chloroacetyl-N-(2,2-diethoxyethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2,3-dimethylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2-methylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2-methylaniline

N-chloroacetyl-N-(2-methoxy-2-methylethyl)-2,6-dimethylaniline

N-(2-ethoxy-2-methylethyl)-N-chloroacetyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1-ethyl-2-methoxyethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2-methoxy-6-methylaniline

N-n-butoxymethyl-N-chloroacetyl-2-tert-butylaniline

N-(2-ethoxyethyl-1-methylethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-methoxyethyl)-2-chloro-6-methylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2-chloro-6-methylaniline

N-(2-ethoxyethyl)-N-chloroacetyl-2,3,6-trimethylaniline

N-chloroacetyl-1-(2-methoxyethyl)-2,3,6-trimethylaniline

N-chloroacetyl-N-cyanomethyl-2,6-dimethylaniline

N-but-3-yn-1-yl-N-chloroacetylaniline

N-chloroacetyl-N-propargyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1,3-dioxan-2-ylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-furanylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(2-furanylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(2-tetrahydrofuranylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(N-propargylcarbamoylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(N,N-dimethylcarbamoylmethyl)-2,6-dimethylaniline

N-(n-butoxymethyl)-N-chloroacetyl-2,6-diethylaniline

N-(2-n-butoxyethyl)-N-chloroacetyl-2,6-diethylaniline

N-chloroacetyl-N-(2-methoxy-1,2-dimethylethyl)-2,6-dimethylaniline

N-chloroacetyl-N-isopropyl-2,3-dimethylaniline

N-chloroacetyl-N-isopropyl-2-chloroaniline

N-chloroacetyl-N-(1H-pyrazol-1-ylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(1H-pyrazol-1-ylmethyl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(1H-1,2,4-triazol-1-ylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(1H-1,2,4-triazol-1-ylmethyl)-2,6-diethylaniline

N-benzoylmethyl-N-chloroacetyl-2,6-dimethylaniline

N-benzoylmethyl-N-chloroacetyl-2-ethyl-6-methylaniline

N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2,6-diethylaniline

N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-ethyl-6-methylaniline

N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-tert-butylaniline

N-chloroacetyl-N-(4-chlorobenzoylmethyl)-2,6-dimethylaniline

N-chloroacetyl-N-(1-methyl-5-methylthio-1,3,4-triazol-2-ylmethyl)-2,6-diethylaniline.

Further haloacetanilides whose harmful effects on cultivated plants canbe antagonised by the novel oxime ethers of the formula I are listed inR. Wegler, Chemie der Pflanzenschutz- and Schadlingsbekampfungsmittel,Vol. 8, pp. 90-93 and pp. 322-327.

Numerous herbicidal thiocarbamates whose phytotoxic action on cultivatedplants can be antagonised by the novel oxime ethers of the formula I arealso known (q.v. for example U.S. Pat. Nos. 2 913 327, 3 037 853, 3 175897, 3 185 720, 3 198 786, 3 582 314 and 3 846 115). The protectiveaction of the novel oxime ethers of the formula I can be utilisedparticularly when applying thiocarbamates in cereals, rice or sorghum.

The thiocarbamates against whose phytotoxic action cultivated plantssuch as cereals, rice and sorghum may particularly be protected, havethe general formulae VIII and IX ##STR11## wherein R₇ is lower alkyl,alkenyl, chloroallyl, dichloroallyl, trichloroallyl, benzyl or4-chlorobenzyl, R₈ is C₂ -C₄ alkyl and R₉ is C₂ -C₄ alkyl or cyclohexyl,and R₈ and R₉ together with the nitrogen atom to which they are attachedcan form a hexahydro-1H-azepine, decayhydroquinoline or2-methyldecahydroquinoline ring.

Typical individual representatives of such thiocarbamates are:

S-ethyl-N,N-dipropylthiocarbamate

S-ethyl-N,N-diisobutylthiocarbamate

S-2,3-dichloroallyl-N,N-diisopropylthiocarbamate

S-propyl-N-butyl-N-ethylthiocarbamate

S-2,3,3-trichloroallyl-N,N-diisopropylthiocarbamate

S-propyl-N,N-dipropylthiocarbamate

S-ethyl-N-ethyl-N-cyclohexylthiocarbamate

S-ethyl-N-hexahydro-1H-azepine-1-carbothioate

S-isopropyl-N,N-hexamethylene-thiocarbamate

S-(p-chlorobenzyl)-N,N-diethylthiocarbamate

N-ethylthiocarbonyl-cis-decahydroquinoline

N-propylthiocarbonyl-decahydroquinaldine

S-ethyl-N,N-bis(n-butyl)-thiocarbamate

S-tert-butyl-N,N-bis(n-propyl)-thiocarbamate.

The amount of antidote employed varies from about 0.01 to about 15 partsby weight per part by weight of herbicide. The most suitable ratio inrespect of optimum action on the particular cultivated plant isestablished from case to case, i.e. depending on the type of herbicideemployed.

The compounds of the formula I are used in unmodified form or,preferably, together with the adjuvants conventionally employed in theart of formulation, and are therefore formulated in known manner toemulsifiable concentrates, coatable pastes, directly sprayable ordilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts, granulates, and also encapsulations in e.g. polymersubstances. As with the nature of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering orpouring, are chosen in accordance with the intended objectives and theprevailing circumstances.

The formulations, i.e. the compositions containing the compound (activeingredient) of the formula I and, where appropriate, a solid or liquidadjuvant, are prepared in known manner, e.g. by homogeneously mixingand/or grinding the active ingredients with extenders, e.g. solvents,solid carriers and, where appropriate, surface-active compounds(surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, e.g. xylene mixtures or substitutednaphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate,aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols andglycols and their ethers and esters, such as ethanol, ethylene glycolmonomethyl or monoethyl ether, ketones such as cyclohexanone, stronglypolar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide ordimethylformamide, as well as epoxidised vegetable oils such asepoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. In addition, a great number of pregranulated materialsof inorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of the formula I to beformulated, suitable surface-active compounds are nonionic, cationicand/or anionic surfactants having good emulsifying, dispersing andwetting properties. The term "surfactants" will also be understood ascomprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained e.g. from coconutoil or tallow oil. Mention may also be made of fatty acid methyltaurinsalts.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metalsalts, alkaline earth metal salts or unsubstituted or substitutedammoniums salts and contain a C₈ -C₂₂ alkyl radical which also includesthe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt oflignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcoholsulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfuric acid esters and sulfonic acids of fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and one fatty acid radicalcontaining 8 to 22 carbon atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolamine salts of dodecylbenzenensulfonicacid, dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonicacid/formaldehyde condensation product. Also suitable are correspondingphosphates, e.g. salts of the phosphoric acid ester of an adduct ofp-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, or saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol, ethylenediamine propyleneglycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms inthe alkyl chain, which adducts contain 20 to 250 ethylene glycol ethergroups and 10 to 100 propylene glycol ether groups. These compoundsusually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitanand polyoxyethylene sorbitan trioleate are also suitable non-ionicsurfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, lower unsubstituted or halogenated alkyl, benzylor lower hydroxyalkyl radicals. The salts are preferably in the form ofhalides, methylsulfates or ethylsulfates, e.g. stearyltrimethylammoniumchloride or benzyldi(2-chloroethyl)ethylammmonium bromide.

The surfactants customarily employed in the art of formulation aredescribed e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MCPublishing Corp. Ringwood, N.J., 1979, and Sisely and Wood,"Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc.New York, 1964.

The pesticidal formulations usually contain 0.1 to 95%, preferably 0.1to 80%, of a compound of the formula I, 1 to 99.9% of a solid or liquidadjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant.

Preferred formulations are composed in particular of the followingconstituents (%=percentage by weight):

    ______________________________________                                        Emulsifiable concentrates                                                     active ingredient                                                                             1 to 20%, preferably 5 to 10%                                 surfactant      5 to 30%, preferably 10 to 20%                                liquid carrier  50 to 94%, preferably 70 to 85%                               Dusts                                                                         active ingredient                                                                             0.1 to 10%, preferably 0.1 to 1%                              solid carrier   99.9 to 90%, preferably 99.9 to 99%                           Suspension concentrates                                                       active ingredient                                                                             5 to 75%, preferably 10 to 50%                                water           94 to 25%, preferably 90 to 30%                               surfactant      1 to 40%, preferably 2 to 30%                                 Wettable powders                                                              active ingredient                                                                             5 to 90%, preferably 1 to 80%,                                surfactant      0.5 to 20%, preferably 1 to 15%                               solid carrier   5 to 95%, preferably 15 to 90%                                Granulates                                                                    active ingredient                                                                             0.5 to 30%, preferably 3 to 15%                               solid carrier   99.5 to 70%, preferably 97 to 85%.                            ______________________________________                                    

Whereas commercial products will be preferably formulated asconcentrates, the end user will normally employ dilute formulations. Theformulations can be diluted to a concentration as low as 0.001%. Therates of application are normally 0.1 to 10 kg a.i./ha, preferably 0.025to 5 kg a.i./ha.

The compositions may also contain further ingredients such asstabilisers, antifoams, viscosity regulators, binders, adhesives, aswell as fertilisers or other active compounds, in order to attainspecial effects.

The invention is illustrated in more detail by the following Examples.

EXAMPLE 1 Preparation of1-phenyl-1-cyanomethoximino-2,2,2-trifluoroethane (compound 4) ##STR12##

19 g (0.1 mole) of 1-(hydroximino)-1-phenyl-2,2,2-trifluoroethane arestirred into a solution of 2.3 g (0.1 mole) and the solvent is removedby evaporation. The residue is dissolved in 50 ml of dimethylsulfoxideand 15.1 g (0.2 mole) of chloroacetonitrile are added dropwise to thesolution. When the addition of chloroacetonitrile is complete, thereaction mixture is initially stirred for 4 hours at 60°-70° C. and thenpoured into ice/water. The organic phase is extracted with methylenechloride. The extract is dried and the solvent removed by evaporation,affording 12.1 g (53.1% of theory) of crystalline title compound, whichhas a melting point of 54°-56° C. after recrystallisation fromisopropanol.

Analysis: calculated: C 52.64%, H 3.09%, N 12.38%, F 24.98%; found: C52.3%, H 3.2%, N 12.4%, F 24.4%.

The following compounds are prepared in corresponding manner:

    __________________________________________________________________________     ##STR13##                                                                    No.                                                                              Phenyl substitution                                                                     X    Q               Physical data (°C.)                  __________________________________________________________________________    1  --        CF.sub.3                                                                           CH.sub.3        b.p. 30-31°/                                                           0.08 mbar                                   2  --        CF.sub.3                                                                           C.sub.3 H.sub.7 n                                                                             b.p. 40-41°/                                                           0.08 mbar                                   3  --        CF.sub.3                                                                           CH.sub.2 CCH    b.p- 50-54°/                                                           0.03 mbar                                   4  --        CF.sub.3                                                                           CH.sub.2 CN     m.p. 54-56°                          5  --        CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                                                           m.p. 84-86°                          6  --        CF.sub.3                                                                           CON(CH.sub.3)CH.sub.2 CN                                                                      n.sub.D.sup.20 1.4960                       7  --        CF.sub.3                                                                           CONHCH.sub.3    m.p. 94-96°                          8  --        CF.sub.3                                                                           COC(Cl)C(Cl).sub.2                                                                            n.sub.D.sup.20 1.5210                       9  --        CF.sub.3                                                                           CONHC(CH.sub.3).sub.3                                                                         m.p. 113-115°                        10 --        CF.sub.3                                                                           CH.sub.2 OCOC(CH.sub.3).sub.3                                                                 b.p. 79-80°/                                                           0.07 mbar                                   11 4-F       CF.sub.3                                                                           CH.sub.3        b.p. 63-64°/                                                           14 mbar                                     12 4-F       CF.sub.3                                                                           C.sub.3 H.sub.7 n                                                                             b.p. 82-84°/                                                           12 mbar                                     13 4-F       CF.sub.3                                                                           CH.sub.2 CN     b.p. 119-122°/                                                         12 mbar                                     14 4-F       CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                                                           m.p. 52-54°                          15 4-Cl      CF.sub.3                                                                           CON(CH.sub.3)CH.sub.2 CN                                                                      wax-like                                    16 4-Cl      CF.sub.3                                                                           CON(CH.sub.3)C.sub.2 H.sub.4 CN                                                               wax-like                                    17 4-Cl      CF.sub.3                                                                           COC.sub.6 H.sub.4 CH.sub.3 (2)                                                                n.sub.D.sup.20 1.5155                       18 4-Cl      CF.sub.3                                                                           COC.sub.6 H.sub.4 CF.sub.3 (3)                                                                n.sub.D.sup.20 1.4900                       19 4-Cl      CF.sub.3                                                                           CONHC(CH.sub.3).sub.3                                                                         m.p. 121-122°                        20 4-Cl      CF.sub.3                                                                           CONHCH.sub.3    m.p. 85-89°                          21 4-Cl      CF.sub.3                                                                           CH.sub.2 CN     oil n.sub.D.sup.24 = 1.4930                 22 4-Cl      CF.sub.3                                                                           COC.sub.6 H.sub.5                                           23 3-Cl      CClF.sub.2                                                                         CH.sub.3                                                    24 --        CClF.sub.2                                                                         C.sub.3 H.sub.7n                                            25 4-Br      CClF.sub.2                                                                         CH.sub.2 CHCH.sub. 2                                        26 4-NO.sub.2                                                                              CClF.sub.2                                                                         CH.sub.3                                                    27 4-CF.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 CN                                                 28 4-OCF.sub.3                                                                             CF.sub.3                                                                           CH.sub.3                                                    29 4-C.sub.4 H.sub.9                                                                       CF.sub.3                                                                           CH.sub.2 CN                                                 30 --        C.sub.2 F.sub.5                                                                    COC.sub.6 H.sub.4 Cl(4)                                     31 --        C.sub.2 F.sub.5                                                                    CH.sub.3                                                    32 --        C.sub.2 F.sub.5                                                                    CONH.sub.2                                                  33 --        C.sub.2 F.sub.5                                                                    CH.sub.2 CN                                                 34 4-Cl      C.sub.2 F.sub.5                                                                    CH.sub.3                                                    35 4-Cl      C.sub.2 F.sub.5                                                                    CH.sub.3                                                    36 4-Cl      C.sub.2 F.sub.5                                                                    COCH.sub.3                                                  37 4-OCH.sub.3                                                                             CF.sub.3                                                                           CH.sub.3                                                    38 4-OCH.sub.3                                                                             CF.sub.3                                                                           C.sub.3 H.sub.7n                                            39 4-OCH.sub.3                                                                             CF.sub.3                                                                           CH.sub.2CHCH.sub.2                                          40 4-OCH.sub.3                                                                             CF.sub.3                                                                           CH.sub.2 CN                                                 41 4-OCF.sub.3                                                                             CF.sub.3                                                                           CH.sub.3                                                    42 4-OCF.sub.3                                                                             CF.sub.3                                                                           CH.sub.2 CN                                                 43 4-OCF.sub.3                                                                             CF.sub.2 Cl                                                                        C.sub.3 H.sub.7n                                            44 3-Cl      CF.sub.3                                                                           CH.sub.3                                                    45 2-Cl      CF.sub.3                                                                           CH.sub.2 CN     73-74° C./0.1                        46 3-Cl      CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         47 3-Cl      CF.sub.3                                                                           CH.sub.2CHCH.sub.2                                          48 3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2 CN                                                 49 3-NO.sub. 2                                                                             CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         50 3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2 C(CH.sub.3).sub.3                                  51 3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2CHCH.sub.2                                          52 2-Cl      CF.sub.3                                                                           C.sub.3 H.sub.7 n                                           53 2-Cl      CF.sub.3                                                                           C.sub.2 H.sub.4 CN                                          54 2-Cl      CF.sub.3                                                                           CH.sub.2CClC(Cl).sub.2                                      55 2-Cl      CF.sub.3                                                                           CONHCH.sub.3                                                56 4-Br      CF.sub.3                                                                           C.sub.3 H.sub.7 i                                           57 4-Br      CF.sub.3                                                                           CH.sub.2 (C(CH.sub.3).sub.3                                 58 4-Br      CF.sub.3                                                                           CH.sub.2 CN                                                 59 4-Br      CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         60 4-CF.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 CONHCH.sub.3                                       61 4-CF.sub.3                                                                              CF.sub.3                                                                           CH(CH.sub.3)CN                                              62 4-CF.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         63 4-CF.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 C(CH.sub.3)CH.sub.2                                64 4-Cl      CF.sub.3                                                                           C.sub.2 H.sub.4COOC.sub.2 H.sub.5                           65 4-OCHF.sub.2                                                                            CF.sub.3                                                                           CH.sub.2 CN                                                 66 4-OCHF.sub.2                                                                            CF.sub.3                                                                           CH.sub.2 COOCH.sub.3                                        67 4-OCHF.sub.2                                                                            CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         68 --        CF.sub.3                                                                           CH.sub.2CH.sub.2N(CH.sub.3).sub.2                                                             57-57° C./0.08                       69 --        CF.sub.3                                                                            ##STR14##      87-90° C./0.09                       70 --        CF.sub.3                                                                           CH.sub.2CHCH.sub.2                                          71 --        CF.sub.3                                                                           CH.sub.2CHCHCH.sub.3                                                                          55-57° C./0.1                        72 --        CF.sub.3                                                                           CH(CH.sub.3)CONH.sub.2                                                                        n.sub.D.sup.24 = 1.4950                     73 4-F       CF.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                            38-40° C./0.15                       74 4-F       CF.sub.3                                                                           CH.sub.2CCH     55-56° C./0.9                        75 4-F       CF.sub.3                                                                           CONHCH.sub.3                                                76 4-F       CF.sub.3                                                                           CONHC(CH.sub.3).sub.3                                       77 4-F       CF.sub.3                                                                           CONHC.sub.3 H.sub.7 (n)                                     78 4-F       CF.sub.3                                                                           CON(CH.sub.3)CH.sub.2CN                                     79 4-Cl      CF.sub.3                                                                           CONHC.sub.3 H.sub.7 (n)                                                                       wax-like                                    80 4-Cl      CF.sub.3                                                                           CH.sub.3        80° C./19                            81 4-Cl      CF.sub.3                                                                           C.sub.3 H.sub.7 (n)                                                                           oil                                         82 4-Cl      CF.sub.3                                                                           CH.sub.2CCH     55-59° C./0.2                        83 4-Cl      CF.sub.3                                                                           CH.sub.2CHCH.sub.2                                                                            53-56° C./0.03                       84 4-Cl      CF.sub.3                                                                           CH.sub.2CONH.sub.2                                                                            m.p. 63-65° C.                       85 4-Cl      CF.sub.3                                                                           CH(CH.sub.3)CONH.sub.2                                                                        m.p. 79-81° C.                       86 4-Cl      CF.sub.3                                                                            ##STR15##                                                  87 4-Cl      CF.sub.3                                                                           CH.sub.2CH.sub.2N(CH.sub.3).sub.2                           88 4-Cl      CF.sub.3                                                                            ##STR16##                                                  89 3-Cl      CF.sub.3                                                                           CH.sub.2 COOC.sub.6 H.sub.5                                 90 3-Cl      CF.sub.3                                                                           CH.sub.2 COOC(CH.sub.3).sub.2                               91 3-Cl      CF.sub.3                                                                           CH.sub.2 COOCH.sub.2 CHCH.sub.2                             92 3,4-Cl.sub.2                                                                            CF.sub.3                                                                           CH(CH.sub.3)COONa                                           93 3,4-Cl.sub.2                                                                            CF.sub.2 Cl                                                                        CH(CH.sub.3)COOK                                            94 3,4-Cl.sub.2                                                                            CF.sub.3                                                                           CH(CH.sub.3)CHCHCOOCH.sub.3                                 95 3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2 CHCHCOOCH.sub.3                                    96 3-NO.sub.2                                                                              CF.sub.3                                                                           CH(CH.sub.3)CHCHCOSCH.sub.3                                 97 3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2 COOCH.sub.2 CN                                     98 3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2 COSCH.sub.2 CHCH.sub.2                             99 3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2 COOC.sub.6 H.sub.5                                 100                                                                              3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2 COSCH.sub.2 CCH                                    101                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2CHCHCOSCH.sub.3                                     102                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2CHCHCOOCH.sub.3                                     103                                                                              3,4-Cl.sub.2                                                                            CF.sub.3                                                                           CH.sub.2 COOCH.sub.2 CHCH                                   104                                                                              3,4-Cl.sub.2                                                                            CF.sub.3                                                                           CH.sub.2 CONHCHO                                            105                                                                              3,4-Cl.sub.2                                                                            CF.sub.3                                                                           CH.sub.2 CONHNH.sub.2                                       106                                                                              3,4-Cl.sub.2                                                                            CF.sub.3                                                                           CH(CH.sub.3)NHNH.sub.2                                      107                                                                              3,4-Cl.sub.2                                                                            CF.sub.3                                                                           CH.sub.2CSNHCH.sub.2CHCH.sub.2                              108                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH.sub.2CONHCONHC.sub.6 H.sub.5                             109                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH.sub.2CONHCONHC.sub.6 H.sub.4 Cl(4)                       110                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH(CH.sub.3)CONHCON(CH.sub.3).sub.2                         111                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 CONHNH.sub.2                                       112                                                                              4-OCH.sub.3                                                                             CF.sub.2 Cl                                                                        COCH.sub.3                                                  113                                                                              4-OCH.sub.3                                                                             CF.sub.2 Cl                                                                        COC.sub.2 H.sub.5                                           114                                                                              4-OCH.sub.3                                                                             CF.sub.2 Cl                                                                        COC.sub.3 H.sub.7 n                                         115                                                                              4-OCH.sub.3                                                                             CF.sub.2 Cl                                                                        COC.sub.4 H.sub.9 t                                         116                                                                              4-OCH.sub.3                                                                             CF.sub.2 Cl                                                                        COC.sub.3 H.sub.7 i                                         117                                                                              4-OCH.sub.3                                                                             CF.sub.2 Cl                                                                        COCHC(CH.sub.3).sub.2                                       118                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH.sub.2 Cl                                               119                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COC(CH.sub.3).sub.2 CH.sub.2 Cl                             120                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCF.sub.3                                                  121                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COC(Cl)CCl.sub.2                                            122                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCOOC.sub.2 H.sub.5                                        123                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCOOC.sub.2 H.sub.5                                        124                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCONH.sub.2                                                125                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH.sub.2 OCH.sub.3                                        126                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH.sub.2 OC.sub.6 H.sub.5                                 127                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH(CH.sub.3)OC.sub.6 H.sub.5                              128                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH(CH.sub.3)OC.sub.6 H.sub.4 Cl(4)                        129                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH(CH.sub.3)OC.sub.6 H.sub.4 Cl(2)                        130                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH.sub.2 OC.sub.6 H.sub.3 Cl.sub.2 (2,4)                  131                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH(CH.sub.3)C.sub.6 H.sub.3 Cl(2)CH.sub.3 (4)             132                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH.sub.2 SC.sub.6 H.sub.5                                 133                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH(CH.sub.3)SC.sub.6 H.sub.5 Cl(4)                        134                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH.sub.3 C.sub.6 H.sub.5                                  135                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH.sub.2 C.sub.6 H.sub.4 Cl                               136                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH(C.sub.3 H.sub.7 i)C.sub.6 H.sub.5                      137                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COCH(C.sub.3 H.sub.7 i)C.sub.3 H.sub.4 Cl(4)                138                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COcyclopropyl                                               139                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           CO1-methylcyclo-                                                              propyl                                                      140                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           CO2,2-dimethyl-                                                               cyclopropyl                                                 141                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           CO2,2 dichlorocyclo-                                                          propyl                                                      142                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COcyclopentyl                                               143                                                                              2-Cl, 4-CH.sub.3                                                                        CF.sub.3                                                                           COcyclohexyl                                                144                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.5                                           145                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 (CH.sub.3)(2)                             146                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 (CH.sub.3)(3)                             147                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 Cl(4)                                     148                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 (CF.sub.3)(3)                             149                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 (CF.sub.3)(2)                             150                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 (OCF.sub.3)(4)                            151                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 (NO.sub.2)(2)                             152                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 Cl(3)                                     153                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub. 4 (OCH.sub.3)(4)                           154                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.4 (OCOCH.sub.3)(2)                          155                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.3 (Cl.sub.2)(3,4)                           156                                                                              2-Br      CF.sub.2 Cl                                                                        COC.sub.6 H.sub.3 (NO.sub.2)(3)(CH.sub.3)(4)                157                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.5                                                                    nicotinoyl                                                  158                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.5                                                                    isonicotinoyl                                               159                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.5                                                                    2,6-dichloroiso-                                                              nicotinoyl                                                  160                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.5                                                                    3-furoyl                                                    161                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.5                                                                    thienyl-2-carbonyl                                          162                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.3                                                                    4-methyl-1,2,3-thia-                                                          diazole-5-carbonyl                                          163                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.3                                                                    3,5-dimethyl-1,2-                                                             oxazolyl-2-carbonyl                                         164                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.3                                                                    2,5-dimethylfuroyl-                                                           2-carbonyl                                                  165                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.3                                                                    2-methyl-4,5-dihydro-                                                         pyranyl-3-carbonyl                                          166                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.3                                                                    3-methyl-2,3-dihydro-                                                         1,4-thioxinyl-2-                                                              carbonyl                                                    167                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.3                                                                    3-methyl-2,3-dihydro-                                                         1-oxo-1,4-thioxinyl-                                                          2-carbonyl                                                  168                                                                              3-NO.sub.2                                                                              C.sub.2 F.sub.3                                                                    2,4-dimethyl-1,4-                                                             thiazolyl-2-carbonyl                                        169                                                                              2,4-Br.sub.2                                                                            CF.sub.3                                                                           1,4-thiazolyl-2-                                                              carbonyl                                                    170                                                                              2,4-Br.sub.2                                                                            CF.sub.3                                                                           1,4-dichloropyr-                                                              imidinyl-5-carbonyl                                         171                                                                              2,4-Br.sub. 2                                                                           CF.sub.3                                                                           3-bromo-2-furoyl                                            172                                                                              2,4-Br.sub.2                                                                            CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.5                                    173                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 Cl(4)                              174                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.3 Cl.sub.2 (2,4)                     175                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 Br(4)                              176                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 (CN)(4)                            177                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 (CH.sub.3)(4)                      178                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 (C.sub.3 H.sub.7 i)(4)             179                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 F(2)                               180                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.3 F.sub.2 (2,6)                      181                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 (NO.sub.2)(4)                      182                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 (OCH.sub.3)(3)                     183                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           C.sub.2 H.sub.4 C.sub.6 H.sub.5                             184                                                                              2-Cl, 4-Br                                                                              CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.5 (C.sub.6 H.sub.5)(4)               185                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHCH.sub.3                                                186                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONH.sub.2                                                  187                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHC.sub.2 H.sub.5                                         188                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHC.sub.6 H.sub.5                                         189                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHC.sub.6 H.sub.3 (CH.sub.3).sub.2 (2,6)                  190                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHcyclohexyl                                              191                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHC.sub.3 H.sub.7 n                                       192                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHC.sub.3 H.sub.7 i                                       193                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHC.sub.6 H.sub.4 Cl(4)                                   194                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHC.sub.4 H.sub.9 t                                       195                                                                              4-OCH.sub.3                                                                             C.sub.3 H.sub.4 F.sub.3                                                            CONHC.sub.6 H.sub.4 (OC.sub.2 H.sub.5)(4)                   196                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           CONHC.sub.6 H.sub.4 (CF.sub.3)(3)                           197                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           CSNHC.sub.6 H.sub.5                                         198                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           CSNHC.sub.6 H.sub.4 (CH.sub.3)(4)                           199                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           SO.sub.2 CH.sub.3                                           200                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           SO.sub.2 CH.sub.2 Cl                                        201                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           SO.sub.2 C.sub.6 H.sub.5                                    202                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           SO.sub.2 N(CH.sub. 3).sub.2                                 203                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           SO.sub.2 C.sub.6 H.sub.4 Cl(4)                              204                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           SO.sub.2 C.sub.6 H.sub.4 (CH.sub.3)(4)                      205                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           piperidinosulfonyl                                          206                                                                              4-OCF.sub.3                                                                             CF.sub.3                                                                           morpholinosulfonyl                                          207                                                                              4-OCH.sub.3                                                                             CF.sub.3                                                                           piperidylsulfonyl                                           208                                                                              4-Cl      CF.sub.2 Cl                                                                        succinimidomethyl                                           209                                                                              4-Cl      CF.sub.3                                                                           2,3-dimethylmaleyl-                                                           imidomethyl                                                 210                                                                              --        CF.sub.3                                                                           succinimidomethyl                                           211                                                                              --        CF.sub.3                                                                           2,3-dimethylmaleyl-                                                           imidomethyl                                                 212                                                                              4-Cl      CF.sub.3                                                                           maleylimidomethyl                                           213                                                                              --        CF.sub.3                                                                           maleylimidomethyl                                           214                                                                              4-Cl      CF.sub.3                                                                           phthalimidomethyl                                           215                                                                              --        CF.sub.3                                                                           phthalimidomethyl                                           216                                                                              4-Cl      CF.sub.3                                                                           3,4,5,6-tetrahydro-                                                           phthalimidomethyl                                           217                                                                              4-Cl      CF.sub.3                                                                           1,2,3,4-tetrahydro-                                                           phthalimidomethyl                                           218                                                                              --        CF.sub.3                                                                           3,4,5,6-tetrahydro-                                                           phthalimidomethyl                                           219                                                                              --        CF.sub.3                                                                           1,2,3,4-tetrahydro                                                            phthalimidomethyl                                           220                                                                              4-Cl      CF.sub.3                                                                           SO.sub.2 N(C.sub.3 H.sub.7 i)CH.sub.2 OCH.sub.3             221                                                                              4-Cl      CF.sub.3                                                                           SO.sub.2 N(CH.sub.3)CH.sub.2 OCH.sub.3                      222                                                                              4-Cl      CF.sub.3                                                                           SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 OCH.sub.3               223                                                                              4-Cl      CF.sub.3                                                                           SO.sub.2 CCl.sub.3                                          224                                                                              4-Cl      CHF.sub.2                                                                          CH.sub.2 CN                                                 225                                                                              4-Cl      CHF.sub.2                                                                          CH(CH.sub.3)CN                                              226                                                                              4-Cl      CHF.sub.2                                                                          CH.sub.2 CONH.sub.2                                         227                                                                              4-Cl      CHF.sub.2                                                                          CH(CH.sub.3)CONH.sub.2                                      228                                                                              4-Cl      CF.sub.3                                                                           2,4,6-trichloro-                                                              pyridino                                                    229                                                                              4-Cl      CHF.sub.2                                                                          2,4,6-trichloro-                                                              pyridino                                                    230                                                                              4-Cl      CF.sub.3                                                                           2,4,6-tribromo-                                                               pyridino                                                    231                                                                              4-Cl      CF.sub.3                                                                           3,5-dichloropyridino                                        232                                                                              4-Cl      CF.sub.3                                                                           3,5-dichloropyridino                                        233                                                                              4-Cl      CF.sub.3                                                                           5-chloro-3-trifluoro-                                                         methylpyridino                                              234                                                                              4-Cl      CHF.sub.2                                                                          5-chloro-3-trifluoro-                                                         methylpyridino                                              235                                                                              4-OCH.sub.3                                                                             CF.sub.3                                                                           CH.sub.2 CN                                                 236                                                                              4-OCH.sub.3                                                                             CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         237                                                                              --        CF.sub.3                                                                           2,4,6-trichloro-                                                              pyridino                                                    238                                                                              --        CF.sub.3                                                                           3,5-dichloropyridino                                        239                                                                              --        CF.sub.3                                                                           5-chloro-3-trifluoro-                                                         methylpyridino                                              240                                                                              --        CF.sub.3                                                                           SO.sub.2 N(CH.sub.3)CH.sub.2 OCH.sub.3                      241                                                                              --        CF.sub.3                                                                           SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 OCH.sub.3               242                                                                              --        CF.sub.3                                                                           SO.sub.2 N(C.sub.3 H.sub.7 i)CH.sub.2 OCH.sub.3             243                                                                              --        CF.sub.3                                                                           SO.sub.2 CCl.sub.3                                          244                                                                              --        CHF.sub.2                                                                          CH.sub.2 CN                                                 245                                                                              --        CHF.sub.2                                                                          CH.sub.2 OCH.sub.3                                          246                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2CCI                                                 247                                                                              --        CF.sub.3                                                                           CH.sub.2CCI                                                 248                                                                              --        CF.sub.3                                                                           C.sub.2 H.sub.4 OH                                          249                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2COOCH.sub.3                                                                           78-80° C./0.06                       250                                                                              --        CF.sub.3                                                                           C.sub.2 H.sub.4 OH                                          251                                                                              4-Cl      CF.sub.3                                                                           C.sub.2 H.sub.4 OH                                          252                                                                              --        CF.sub.3                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                 253                                                                              4-Cl      CF.sub.3                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                 254                                                                              --        CF.sub.3                                                                           C.sub.2 H.sub.4 OCONHCH.sub.3                               255                                                                              4-Cl      CF.sub.3                                                                           C.sub.2 H.sub.4 OCONHCH.sub.3                               256                                                                              --        CF.sub.3                                                                           C.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                        257                                                                              4-Cl      CF.sub.3                                                                           C.sub.2 H.sub.4 OCH.sub.2 CHCH.sub.2                        258                                                                              3-CF.sub.3                                                                              CF.sub.3                                                                            ##STR17##      b.p. 57-57° C./ 0.08 mbar            259                                                                              3-CF.sub.3                                                                              CF.sub.3                                                                           CH.sub.2CONH.sub.2                                                                            wax-like                                    260                                                                              --        C.sub.2 F.sub.5                                                                    CH.sub.2CONH.sub.2                                                                            b.p. 90-100°/                                                          0.05 mbar                                   261                                                                              3-CF.sub.3                                                                              CF.sub.3                                                                           CH(CH.sub.3)CONH.sub.2                                                                        b.p. 102- 111°/                                                        0.08 mbar                                   262                                                                              4-F       CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 F(2)                                                                 b.p. 81-83°/                                                           0.03 mbar                                   263                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 F(2)                                                                 b.p. 95-96°/                                                           0.08 mbar                                   264                                                                              4-F       CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 F(4)                                                                 b.p. 76-77°/                                                           0.04 mbar                                   265                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.4 F(4)                                                                 b.p. 95-97°/                                                           0.05 mbar                                   266                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 CN     b.p. 83-84°/                                                           0.1 mbar                                    267                                                                              4-F       CF.sub.3                                                                           CH.sub.2 CN     b.p. 119-122°/                                                         12 mbar                                     268                                                                              4-Cl      CF.sub.3                                                                            ##STR18##                                                  269                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2CONHCH.sub.3                                        270                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 CON(CH.sub.3).sub.2                                271                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 CONHC.sub.2 H.sub.5                                272                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 COOC.sub.2 H.sub.5                                 273                                                                              4-Cl      CF.sub.3                                                                           CH(CH.sub.3)COOC.sub.2 H.sub.5                              274                                                                              2-Cl      CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                                                           m.p. = 70-73° C.                     275                                                                              2-Cl      CF.sub.3                                                                           CH(CH.sub.3)CONH.sub.2                                                                        b.p. = 121-123° C./                                                    0.12                                        276                                                                              2-Cl      CF.sub.3                                                                           CH.sub.2 COOC.sub.2 H.sub.5                                 277                                                                              2-Cl      CF.sub.3                                                                           CH(CH.sub.3)COOC.sub.2 H.sub.5                              278                                                                              4-Cl      CF.sub.3                                                                           CH(CH.sub.3)COOC.sub.2 H.sub.5                              279                                                                              4-Cl      CF.sub.3                                                                           CH(CH.sub.3)COOC.sub.3 H.sub.7 n                            280                                                                              4-Cl      CF.sub.3                                                                           CH(CH.sub.3)COOCH.sub.2 CHCH.sub.2                          281                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 CSNH.sub.2                                         282                                                                              4-Cl      CF.sub.3                                                                           CH(CH.sub.3)CSNH.sub.2                                      283                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                                                           m.p. = 92-94° C.                     284                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH(CH.sub.2)CONH.sub.2                                                                        m.p. = 76-77° C.                     285                                                                              3,4(CH.sub.3).sub.2                                                                     CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         286                                                                              3,4(CH.sub.3).sub.2                                                                     CF.sub.3                                                                           CH(CH.sub.3)CONH.sub.2                                      287                                                                              --        C.sub.2 H.sub.5                                                                    CH.sub.2 CONH.sub.2                                         288                                                                              --        C.sub.2 H.sub.5                                                                    CH(CH.sub.3)CONH.sub.2                                      289                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 COOCH.sub.3                                        290                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 COOC.sub.3 H.sub.7 n                               291                                                                              4-CH.sub.3                                                                              CF.sub. 3                                                                          CH(CH.sub.3)COOC.sub.2 H.sub.5                              292                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 COSC.sub.2 H.sub.5                                 293                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 COOC.sub.2 H.sub.4 OCH.sub.3                       294                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 COOC.sub.2 H.sub.4 Cl                              295                                                                              4-OCH.sub.3                                                                             CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         296                                                                              3-NO.sub.2                                                                              CF.sub.3                                                                           CH.sub.2 CONH.sub.2                                         297                                                                              4-Cl      CHF.sub.2                                                                          CH.sub.2 CONH.sub.2                                         298                                                                              4-Cl      CHF.sub.2                                                                          CH(CH.sub.3)CONH.sub.2                                      300                                                                              4-Cl      CHF.sub.2                                                                          CH(CH.sub.3)COOC.sub.2 H.sub.5                              301                                                                              4-Cl      CF.sub.3                                                                           SO.sub.2 CF.sub.3                                           302                                                                              4-Cl      CF.sub.3                                                                           SO.sub.2 CHCl                                               303                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2COOC.sub.3 H.sub.7 iso                                                                90-91° C./0.09                       304                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 CONHNH.sub.2                                       305                                                                              4-Cl      CF.sub.3                                                                           CH(CH.sub.3)CONHNH.sub.2                                    306                                                                              4-Cl      CHF.sub.2                                                                           ##STR19##                                                  7  4-Cl      CF.sub.3                                                                           C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                          308                                                                              4-Cl      CF.sub.3                                                                           CH(C.sub.2 H.sub.5)CONH.sub.2                               309                                                                              4-Cl      CF.sub.3                                                                           CH.sub.2 COOCH.sub.2 CF.sub.3                                                                 77-78° C./0.06                       310                                                                              4-F       CF.sub.3                                                                           CH.sub.2 COOCH.sub.2 CF.sub.3                               311                                                                              4-CH.sub.3                                                                              CF.sub.3                                                                           CH.sub.2 COOCH.sub.2 CF.sub.3                               __________________________________________________________________________

EXAMPLE 2 Formulation examples for compounds of formula I or mixturesthereof with herbicides (percentages are by weight)

    ______________________________________                                        (a) Wettable powders                                                                              (a)     (b)      (c)                                      ______________________________________                                        Compound of formula I or mixture                                                                  20%     60%        0.5%                                   thereof with a herbicide                                                      sodium lignosulfonate                                                                             5%      5%       5%                                       sodium laurylsulfate                                                                              3%      --       --                                       sodium diisobutylnaphthalenesulfonate                                                             --      6%       6%                                       octylphenol polyethylene glycol ether                                                             --      2%       2%                                       (7-8 moles of ethylene oxide                                                  highly dispersed silicid acid                                                                     5%      27%      27%                                      kaolin              67%     --       --                                       sodium chloride     --      --        59.5%                                   ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        (b) Emulsifiable concentrate                                                                          (a)    (b)                                            ______________________________________                                        Compound of formula I or mixture thereof                                                              10%    1%                                             with a herbicide                                                              octylphenol polyethylene glycol ether                                                                  3%    3%                                             (4-5 moles of ethylene oxide)                                                 calcium dodecylbenzenesulfonate castor oil                                                             4%    4%                                             polyglycol ether (36 moles of ethylene oxide)                                 cyclohexanone           30%    10%                                            xylene mixture          50%    79%                                            ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        (c) Dusts               (a)     (b)                                           ______________________________________                                        Compound of formula I or mixture thereof                                                               0.1%    1%                                           with a herbicide                                                              talcum                  99.9%   --                                            kaolin                  --      99%                                           ______________________________________                                    

Dusts which are ready for use are obtained by mixing the activeingredient with the carriers, and grinding the mixture in a suitablemill.

    ______________________________________                                        (d) Extruder granulate  (a)    (b)                                            ______________________________________                                        Compound of formula I or mixture thereof                                                              10%    1%                                             with a herbicide                                                              sodium lignosulfonate    2%    2%                                             carboxymethylcellulose   1%    1%                                             kaolin                  87%    96%                                            ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        (e) Coated granulate                                                          ______________________________________                                        Compound of formula I or mixture thereof                                                               3%                                                   with a herbicide                                                              polyethylene glycol 200  2%                                                   kaolin                   94%                                                  ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coatedgranulates are obtained in this manner.

    ______________________________________                                        (f) Suspension concentrate                                                                           (a)       (b)                                          ______________________________________                                        Compound of formula I or mixture thereof                                                             40%       5%                                           with a herbicide                                                              ethylene glycol        10%       10%                                          nonylphenol polyethylene glycol ether                                                                 6%       1%                                           (15 moles of ethylene oxide)                                                  sodium lignosulfonate  10%       5%                                           carboxymethylcellulose  1%       1%                                           37% aqueous formaldehyde solution                                                                      0.2%      0.2%                                       silicone oil in the form of a 75%                                                                      0.8%      0.8%                                       aqueous emulsion                                                              water                  32%       77%                                          ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

    ______________________________________                                        (g) Salt solution                                                             ______________________________________                                        Compound of formula I or mixture thereof                                                               5%                                                   with a herbicide                                                              isopropylamine           1%                                                   octylphenol polyethylene glycol ether                                                                  3%                                                   (78 moles of ethylene oxide)                                                  water                    91%                                                  ______________________________________                                    

Biological Examples

The ability of the compounds of formula I to protect cultivated plantsfrom the phytotoxic effects of potent herbicides is illustrated in thefollowing Examples. In the test procedures the compounds of formula Iare referred to as antidotes (safeners).

EXAMPLE 3

Test with antidote and herbicide in sorghum. Preemergence application ofherbicide and antidote as tank mixture.

Plastic containers measuring 25 cm×17 cm×12 cm are filled with sandyloam and Funk G 522 sorghum seeds are sown therein. The seeds are thenlightly covered with a layer of soil onto which is sprayed a diluteaqueous solution containing the herbicide and the antidote in thedesired ratio. The condition of the plants is assessed 30 days later.The protective action is expressed in percent and indicates the degreeto which the antidote (safener) is able to reduce the phytotoxic actionof the herbicide. A significant effect is achieved in the phytotoxicityif the range of severe to average damage can be reduced to that ofslight, reversible damage or to complete tolerance.

The results are as follows:

Herbicide 2-chloro-6'-ethyl-N-("methoxy-1"-methylethyl)-acet-o-toluidide("metolachlor")

    ______________________________________                                        Antidote        Herbicide   Relative protective action                        No.     kg/ha   kg/ha       in %                                              ______________________________________                                         4      1.5     1.5         25                                                 5      1.5     1.5         13                                                 8      1.5     1.5         25                                                14      1.5     1.5         63                                                71      1.5     1.5         13                                                81      1.5     1.5         38                                                83      1.5     1.5         25                                                84      1.5     1.5         63                                                85      1.5     1.5         13                                                259     1.5     1.5         50                                                261     1.5     1.5         38                                                264     1.5     1.5         38                                                267     1.5     1.5         25                                                ______________________________________                                    

EXAMPLE 4

Preemergence test with antidote and herbicide in sorghum. Application ofthe antidote by seed dressing.

Funk G 522 sorghum seeds are mixed with the antidote in a glass flask.Seeds and compound are thoroughly mixed by shaking and rotating theflask. Finally the dressed seeds are sown in flower pots (diameter atthe top 11 cm) filled with sandy loam. The seeds are covered lightlywith soil onto which an aqueous emulsion of the herbicide is sprayed inthe desired concentration. The condition of the plants is assessed 8days after the treatment with the herbicide and the relative protectiveaction is expressed in percent. The results are as follows:

Herbicide 2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)-acet-o-toluide("metolachlor")

    ______________________________________                                        Antidote          Herbicide Relative protective action                        No.    g/kg seeds kg/ha     in %                                              ______________________________________                                         5     2          4         88                                                 5     1          4         50                                                 5     0.5        4         25                                                 5     2          2         63                                                 5     1          2         50                                                 5     0.5        2         50                                                 5     2          1         75                                                 5     1          1         38                                                 5     0.5        1         38                                                13     2          4         50                                                13     1          4         50                                                13     0.5        4         25                                                13     2          2         75                                                13     1          2         63                                                13     0.5        2         25                                                13     2          1         75                                                13     1          1         63                                                13     0.5        1         38                                                84     2          4         38                                                84     1          4         50                                                84     0.5        4         50                                                84     2          2         38                                                84     1          2         50                                                84     0.5        2         50                                                84     2          1         38                                                84     1          1         50                                                84     1          1         50                                                ______________________________________                                    

EXAMPLE 5

Test with antidote and herbicide in soybeans. Preemergence applicationof herbicide and antidote as tank mixture.

Flower pots (diameter at the top 6 cm) are filled with sandy loam and"Hark" soybean seeds are sown therein. The seeds are covered and adilute solution of the compound for testing as safener, together withthe herbicide, is sprayed as tank mixture onto the surface of the soil.The protective action is evaluated (in %) 21 days after application. Theresult is as follows:

Herbicide 4-amino-3-methylthio-6-tert-butyl-1,2,4-triazin-5-one("metribuzin")

    ______________________________________                                        Antidote        Herbicide   Relative protective action                        No.     kg/ha   kg/ha       in %                                              ______________________________________                                        1       1.5     0.75        50                                                ______________________________________                                    

EXAMPLE 6

Test with antidote and herbicide in wheat. Preemergence application ofherbicide and antidote as tank mixture.

"Farnese" wheat seeds are sown in plastic pots (diameter at the top 11cm) containing 0.5 liter of earth in a greenhouse. The seeds are coveredand the compound for testing as safener is applied, together with theherbicide, as tank mixture. The protective action of the safener isevaluated (in %) 24 days after application. The results are reportedbelow:

Herbicide Propynyl α-[4-(2,4-dichloropyridyl-2-oxy)phenoxy]-propionate

    ______________________________________                                        Antidote        Herbicide   Relative protective action                        No.     kg/ha   kg/ha       in %                                              ______________________________________                                         5      1.5     0.75        38                                                 8      1.5     0.75        25                                                14      1.5     0.75        38                                                72      1.5     0.75        25                                                79      1.5     0.75        38                                                81      1.5     0.75        25                                                84      1.5     0.75        38                                                85      1.5     0.75        38                                                ______________________________________                                    

EXAMPLE 7

Test with antidote and herbicide in maize. Application of the antidoteby seed dressing.

LB 5 maize seeds are mixed together with the safener for testing in aglass beaker. Seeds and compounds are thoroughly mixed by shaking androtation. Plastic pots (diameter at the top 11 cm) are filled with soiland the dressed seeds are sown therein. The seeds are covered and thensome of the herbicides are applied preemergence in substantial overdose.The protective action of the safener is determined in percent 18 daysafter application of the herbicide. The plants treated with herbicidealone and the completely untreated controls are used for referencepurposes. The results are as follows:

Herbicide 2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)acet-o-toluide("metolachlor")

    ______________________________________                                        Antidote          Herbicide Relative protective action                        No.    g/kg seeds kg/ha     in %                                              ______________________________________                                        84     2          6         75                                                84     1          6         75                                                84     1.5        6         75                                                ______________________________________                                    

Herbicide S-ethyl-dipropylthiocarbamate ("EPTC")

    ______________________________________                                        Antidote          Herbicide Relative protective action                        No.    g/kg seeds kg/ha     in %                                              ______________________________________                                        84     2          6         50                                                84     1          6         63                                                84     0.5        6         38                                                84     2          4         63                                                84     1          4         63                                                84     0.5        4         38                                                ______________________________________                                    

Herbicide N-isopentyl-3,4-dimethyl-2,6-dinitroaniline ("penoxalin")

    ______________________________________                                        Antidote          Herbicide Relative protective action                        No.    g/kg seeds kg/ha     in %                                              ______________________________________                                        84     2          4         50                                                84     1          4         50                                                84     0.5        4         25                                                84     2          2         25                                                84     2          2         25                                                84     0.5        2         38                                                ______________________________________                                    

EXAMPLE 8

Test with antidote and herbicide in maize. Preemergence application ofantidote and herbicide as tank mixture.

Plastic containers measuring 25 cm×17 cm×12 cm are filled with sandyloam and LG 5 maize seeds are sown therein. The seeds are covered and adilute solution of the safener for testing, together with an overdose ofherbicide, is applied as tank mixture to the surface of the soil. Theprotective action of the safener is evaluated in percent 21 days afterapplication. The plants treated with herbicide alone as well as thecompletely untreated controls are used for reference purposes. Theresults are as follows:

Herbicide 2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)acet-o-toluide("metolachlor").

    ______________________________________                                        Antidote        Herbicide   Relative protective action                        No.     kg/ha   kg/ha       in %                                              ______________________________________                                        84      3       6           50                                                84      1.5     6           38                                                84      0.75    6           25                                                ______________________________________                                    

EXAMPLE 9

Test with antidote and herbicide in dry sown rice. Preemergenceapplication of herbicide and antidote as tank mixture.

Rice seeds are sown in containers measuring 47 cm×29 cm×24 cm, covered,and the soil is lightly pressed firm. Then a dilute solution of theantidote for testing, together with the herbicide, is sprayed onto thesurface of the soil as tank mixture. The protective action of theherbicide is evaluated in percent 24 days after sowing. The plantstreated with herbicide alone and the completely untreated controls areused for reference purposes. The results are reported below.

Herbicide2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)acet-o-toluidide("metolachlor")

    ______________________________________                                        Antidote        Herbicide   Relative protective action                        No.     kg/ha   kg/ha       in %                                              ______________________________________                                        260     1.5     0.25        25                                                ______________________________________                                    

EXAMPLE 10

Test with antidote and herbicide in dry sown and subsequently floodedrice. Preemergence application of herbicide and antidote as tankmixture.

Rice seeds of the IR-36 variety are sown in containers measuring47×29×24 cm, covered, and the soil is lightly pressed firm. The compoundfor testing as antidote together with the herbicide are then sprayed astank mixture. About 20 days after sowing (when the rice plants are inthe 3-leaf stage), the surface of the soil is covered with water to aheight of 4 cm. The protective action of the antidote is evaluated 30days after application. Plants treated with herbicide alone andcompletely untreated controls are used for reference purposes. Theresults are set forth below.

Herbicide2-chloro-6'-ethyl-N-(2"-methoxy-1"-methylethyl)acet-o-toluidide("metolachlor")

    ______________________________________                                        Antidote        Herbicide   Relative protective action                        No.     kg/ha   kg/ha       in %                                              ______________________________________                                        260     1.5     0.25        25                                                ______________________________________                                    

EXAMPLE 11

Test with antidote and herbicide in rice sown in water. Application ofthe antidote during immersion of the rice seeds. Rice seeds are immersedfor 48 hours in 10, 100 and 1000 ppm solutions of the compound fortesting as safener. The seeds are then allowed to dry for about 2 hoursuntil they are no longer tacky. Plastic containers measuring 25 cm×17cm×12 cm are filled with sandy loam to 2 cm below the edge. Thepretreated seeds are sown on the surface of the soil in the containersand only lightly covered. The soil is kept in a moist (non-marshy)state. Then a dilute solution of the herbicide is sprayed onto thesurface of the soil. The water level is then gradually raised inaccordance with growth of the rice plants. The protective action of thesafener is evaluated (in %) 18 days after application. The plantstreated with herbicide alone and the completely untreated controls areused for reference purposes. The results are as follows:

Herbicide 2-chloro-2',6'-diethyl-N-(2"-propylethyl)acetanilide("pretilachlor").

    ______________________________________                                        Antidote        Herbicide Relative protective action                          No.    ppm      kg/ha     in %                                                ______________________________________                                         18    100      0.25      25                                                  260    100      0.25      50                                                  ______________________________________                                    

What is claimed is:
 1. An oxime ether of the formula I ##STR20## R₁ ishydrogen, halogen C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfinyl, C₁ -C₄alkylsulfonyl, C₁ -C₄ haloalkylsulfonyl or nitro,R₂ and R₃ are eachhydrogen, halogen C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ haloalkyl, Q is--CH₂ CONH₂ or --CH(CH₃)CONH₂ ; and X is a fluorinated C₁ -C₃ alkylradical, which may also contain chlorine.
 2. An oxime ether according toclaim 1 of the formula Ia ##STR21## wherein R₁, Q and X are as definedin claim
 1. 3. An oxime ether according to claim 1 of the formula Ib##STR22## wherein R₁, R₂ and Q are as defined in claim
 1. 4. An oximeether according to claim 1 of the formula Ii ##STR23## wherein R₁ and R₂are as defined in claim
 1. 5. An oxime ether according to claim 1 of theformula Ij ##STR24## wherein R₁ and R₂ are as defined in claim
 1. 6. Anoxime ether according to claim 1, wherein R₁ is hydrogen, halogen,methyl, methoxy, trifluoromethyl or nitro, R₂ is hydrogen, halogen ormethyl, and R₃ is hydrogen. 7.1-Phenyl-1-carbamoylmethoximino-2,2,2-trifluoroethane according to claim1 of the formula ##STR25## 8.1-(4-Fluorophenyl)-1-carbamoylmethoximino-2,2,2-trifluoroethaneaccording to claim 1 of the formula ##STR26## 9.1-(4-Chlorophenyl)-1-carbamoylmethoximino-2,2,2-trifluoroethaneaccording to claim 1 of the formula ##STR27## 11.1-Phenyl-1-carbamoylmethoximino-2,2,3,3,3-pentafluoropropane accordingto claim 1 of the formula ##STR29## 12.1-Phenyl-1-carbamoyleth-1'-oximino-2,2,2-trifluoroethane according toclaim 1 of the formula ##STR30## 13.1-(4-Chlorophenyl)-1-carbamoyleth-1'-oximino-2,2,2-trifluoroethaneaccording to claim 1 of the formula ##STR31## 14.1-(3-Trifluoromethylphenyl)-1-carbamoyleth-1'-oximino-2,2,2-trifluoroethaneaccording to claim 1 of the formula ##STR32##
 15. A composition forprotecting cultivated plants from damage caused by a herbicidalhaloacetanilide, thiocarbamate, 1,2,4-triazinone or dinitroaniline,which composition contains an effective amount of an oxime ether ofclaim 1, together with an inert carrier.
 16. A composition according toclaim 15, which contains(a) an effective amount of a herbicidalhaloacetanilide or a herbicidal thiocarbamate, and (b) an effectiveamount of the oxime ether as antidote, together with a suitable carrier.17. A composition which contains as active components, effective amountsof(a) a haloacetanilide herbicide of the formula ##STR33## wherein Halis chlorine or bromine, each of R₄ and R₅ independently of the other ishydrogen, halogen, lower alkyl, alkoxy, alkylthio, haloalkyl,alkoxyalkyl or alkylthioalkyl, Z is hydrogen or methyl, A is methylene,1,1-ethylene or 1,2-ethylene which may be substituted by 1 or 2 loweralkyl groups, and R₆ is lower alkoxy, hydroxycarbonyl, alkoxycarbonyl,carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, cyano,1H-pyrazol-1-yl, 1H-1,2,4-triazol-1-yl, alkanoyl, 1,3,4-oxadiazol-2-yl,5-methyl-1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl,1,3,4-triazol-3-yl, or 1,3,4-triazol-1-yl, and (b) an oxime ether ofclaim 1 as antidote, together with a suitable carrier.
 18. A compositionaccording to claim 15 which contains(a) a thiocarbamate of the formulaVIII or IX ##STR34## wherein R₇ is lower alkyl, alkenyl, chloroallyl,dichloroallyl, trichloroallyl, benzyl or 4-chlorobenzyl, R₈ is C₂ -C₄alkyl and R₉ is C₂ -C₄ alkyl or cyclohexyl, and R₈ and R₉ together withthe nitrogen atom to which they are attached can form ahexahydro-1H-azepine, decahydroquinoline or 2-methyldecahydroquinolinering, and (b) an oxime ether as antidote, together with a suitablecarrier.
 19. A method of protecting cultivated plants from damage thatmay be caused by the application of a herbicidal haloacetanilide,thiocarbamate, 1,2,4-triazinone or dinitroaniline, which methodcomprises(a) treating the locus of the plant before or duringapplication of the herbicide, or (b) treating the seeds or seedlings ofthe plant itself with an effective amount of an oxime ether of claim 1.